Allyl ester copolymers with allylic alcohols or propoxylated allylic alcohols

ABSTRACT

Allyl ester copolymers with allylic alcohols and propoxylated allylic alcohols are disclosed. The high hydroxyl group content and favorable solubility characteristics make the allyl ester copolymers easy to formulate into many polymer products, including polyurethanes, polyesters, melamines, alkyds, uralkyds, and other thermoset polymers.

FIELD OF THE INVENTION

The invention relates to copolymers of allyl esters and allylic alcoholsor propoxylated allylic alcohols. The copolymers, which have a highconcentration of hydroxyl groups, are useful in many types of curablepolymer systems, such as coatings and adhesives.

BACKGROUND OF THE INVENTION

Allyl alcohol, a well-known monomer, is available commercially fromisomerization of propylene oxide. Ethylenic polymerization of allylicalcohols with other olefins is a potential route to polymers that have ahigh concentration of primary hydroxyl groups. Such copolymers arepotentially valuable polymers intermediates because they will curerapidly with isocyanates, anhydrides, and melamine resins to give usefulthermoset articles.

Few allylic alcohol copolymers have actually become commerciallyimportant. Poly(allyl alcohol), for example, is not widely used in spiteof its high concentration of primary hydroxyl groups because of its poorsolubility in most common organic solvents. Copolymers of allyl alcoholand typical vinyl monomers such as styrene are known, but because allylalcohol reacts much more slowly than vinyl monomers, a large excess ofallyl alcohol is needed in the copolymerization to get a desirablehydroxyl group content.

Allyl ester polymers are known, but because allyl esters polymerizeslowly with even high levels of free-radical initiators to give polymersof only low molecular weight, few allyl esters have any industrial usefor polymers and copolymers (see S. R. Sandler and W. Karo, PolymerSyntheses, Vol. III (1980), Chapter 8, "Polymerization of Allyl Esters,"pp. 248-294, at page 263).

New hydroxy-functional allyl ester copolymers are needed. Particularlyvaluable copolymers would be easy to prepare and would have a highconcentration of hydroxyl groups. Preferably, the copolymers would besoluble in common organic solvents to enable easy formulation intopolyurethanes, polyesters, melamines, alkyd coatings, uralkyds, andother thermoset polymers.

SUMMARY OF THE INVENTION

The invention is an allyl ester/allylic alcohol copolymer. The copolymercomprises recurring units of (a) an allyl ester of the formula CH₂═CR'--CH₂ --O--CO--R in which R is hydrogen or a saturated linear,branched, or cyclic C₁ -C₃₀ alkyl, aryl, or aralkyl group, and R' isselected from the group consisting of hydrogen and C₁ -C₅ alkyl; and (b)an allylic alcohol of the formula CH₂ ═CR'--CH₂ --OH in which R' isselected from the group consisting of hydrogen and C₁ -C₅ alkyl. Thecopolymer has an average hydroxyl functionality within the range ofabout 2 to about 10, and a number average molecular weight within therange of about 300 to about 15,000.

The invention also includes copolymers of the allyl esters describedabove and propoxylated allylic alcohols of the formula CH₂ ═CR'--CH₂--(A)_(n) --OH in which A is an oxypropylene group, R' is selected fromthe group consisting of hydrogen and C₁ -C₅ alkyl, and n, which is theaverage number of oxypropylene groups in the propoxylated allylicalcohol, has a value less than or equal to 2. These copolymers also haveaverage hydroxyl functionalities within the range of about 2 to about10, and number average molecular weights within the range of about 300to about 15,000.

I found that, compared with other allylic alcohol copolymers, those ofthe invention are generally easier to prepare because of the similarmonomeric reactivity ratios. Compared with poly(allyl alcohol), thecopolymers of the invention have much better solubility in commonorganic solvents. The high hydroxyl group content and favorablesolubility characteristics make the allyl ester copolymers easy toformulate into many polymer products, including polyurethanes,polyesters, melamines, alkyds, uralkyds, and other thermoset polymers.

DETAILED DESCRIPTION OF THE INVENTION

Copolymers of the invention comprise recurring units of an allyl esterand an allylic alcohol or a propoxylated allylic alcohol.

Allyl esters suitable in the invention have the general structure: CH₂═CR'--CH₂ --O--CO--R in which R is hydrogen or a saturated linear,branched, or cyclic C₁ -C₃₀ alkyl, aryl, or aralkyl group, and R' isselected from the group consisting of hydrogen and C₁ -C₅ alkyl.Suitable allyl esters include, but are not limited to allyl formate,allyl acetate, allyl butyrate, allyl benzoate, methallyl acetate, andthe like, and mixtures thereof. Particularly preferred are allyl estersderived from allyl alcohol and methallyl alcohol. Most preferred are C₁-C₅ alkyl esters of allyl alcohol and methallyl alcohol.

Allylic alcohols suitable in the invention have the general structure:CH₂ ═CR'--CH₂ --OH in which R' is selected from the group consisting ofhydrogen and C₁ --C₅ alkyl. Suitable allylic alcohols include, but arenot limited to, allyl alcohol, methallyl alcohol, 2-ethyl-2-propen-1-ol,and the like, and mixtures thereof. Allyl alcohol and methallyl alcoholare preferred.

The relative proportions of allyl ester and allylic alcohol in thecopolymer are not critical. The actual proportions used will generallydepend upon many factors, including, for example, the desired hydroxylend group content of the copolymer, the desired solubilitycharacteristics, the identity of the R groups, and other considerations.Generally, the copolymers will comprise from about 1 to about 99 wt. %of the allyl ester and from about 99 to about 1 wt. % of the allylicalcohol. More preferred copolymers will have from about 5 to about 95wt. % of the allyl ester and from about 95 to about 5 wt. % of theallylic alcohol. Most preferred are copolymers which comprise from about30 to about 70 wt. % of the allyl ester and from about 70 to about 30wt. % of the allylic alcohol.

The allyl ester/allylic alcohol copolymers of the invention have averagehydroxyl functionalities within the range of about 2 to about 10,preferably from about 3 to about 6. The copolymers will have numberaverage molecular weights within the range of about 300 to about 15,000.A more preferred range is from about 500 to about 3000.

Preferred allyl ester/allylic alcohol copolymers of the invention willhave hydroxyl numbers within the range of about 10 to about 950 mgKOH/g. A more preferred range is from about 25 to about 500 mg KOH/g.

The invention includes copolymers which comprise recurring units of theallyl esters described above and propoxylated allylic alcohols of theformula CH₂ ═CR'--CH₂ --(A)_(n) --OH in which A is an oxypropylenegroup, R' is selected from the group consisting of hydrogen and C₁ -C₅alkyl, and n, which is the average number of oxypropylene groups in thepropoxylated allylic alcohol, has a value less than or equal to 2. Theoxypropylene groups in the propoxylated allylic alcohols have one orboth of the structures --OCH(CH₃)--CH₂ --and --O--CH₂ --CH(CH₃)--, whichwill depend on the method of synthesis.

Suitable propoxylated allylic alcohols can be prepared by reacting anallylic alcohol with up to about 2 equivalents of propylene oxide in thepresence of a basic catalyst as described, for example, in U.S. Pat.Nos. 3,268,561 and 4,618,703, the teachings of which are incorporatedherein by reference. As will be apparent to those skilled in the art,suitable propoxylated allylic alcohols can also be made by acidcatalysis, as described, for example, in J. Am. Chem. Soc. 71 (1949)1152.

As with the allyl ester/allylic alcohol copolymers, the relativeproportion of monomers used to make the allyl ester/propoxylated allylicalcohol copolymers of the invention is not critical. The copolymerspreferably comprise from about 1 to about 99 wt. % of allyl esterrecurring units, and from about 99 to about 1 wt. % of propoxylatedallylic alcohol recurring units. More preferred copolymers comprise fromabout 5 to about 95 wt. % of allyl ester recurring units, and from about95 to about 5 wt. % of propoxylated allylic alcohol recurring units.Most preferred are copolymers comprising from about 30 to about 70 wt. %of allyl ester recurring units, and from about 70 to about 30 wt. % ofpropoxylated allylic alcohol recurring units.

The allyl ester/propoxylated allylic alcohol copolymers of the inventionhave average hydroxyl functionalities within the range of about 2 toabout 10 (preferably from about 3 to about 6), and number averagemolecular weights within the range of about 300 to about 15,000 (morepreferably from about 500 to about 3000).

Preferred allyl ester/propoxylated allylic alcohol copolymers of theinvention will have hydroxyl numbers within the range of about 10 toabout 480 mg KOH/g. A more preferred range is from about 25 to about 300mg KOH/g.

The allyl ester copolymers of the invention are made by free-radicalpolymerization. The monomers can be simply combined and heated in thepresence of a free-radical initiator at a temperature effective topolymerize the monomers. Suitable free-radical initiators are theperoxide and azo-type initiators well known to those skilled in the art.Peroxide initiators are preferred. Examples include hydrogen peroxide,benzoyl peroxide, di-tert-butylperoxide, tert-butylhydroperoxide,tertbutylperbenzoate, azobis(isobutyronitrile)(AIBN), and the like.

The monomers and free-radical initiator can be combined and reacted inany desired way. We found that improved yields can be achieved, however,if the initiator is added gradually to the reaction mixture during thecourse of the polymerization. Thus, it is preferred to introduce theinitiator either continuously or intermittently to the polymerizationreaction mixture.

The process can be performed at any temperature effective to initiatefree-radical polymerization. Generally, it is preferred to perform thereaction at a temperature within the range of about 90° C. to about 200°C. A more preferred range is from about 125° C. to about 180° C.; mostpreferred is the range of about 135° C. to about 165° C.

The polymerizations can be performed at any suitable pressure.Generally, it is preferred to perform the polymerizations at pressuresgreater than 1 atmosphere, particularly when allyl alcohol is areactant. Particularly preferred is the pressure range from about 20 toabout 500 psi.

Optionally, a solvent is included in the polymerization. Suitablesolvents are those in which the monomers, free-radical initiator, andpolymeric reaction products are soluble. Preferred solvents for thepolymerization include alcohols, ethers, esters, glycols, glycol ethers,and glycol ether esters. Aliphatic hydrocarbons are generally notsuitable because the polymer products are usually not soluble inaliphatic hydrocarbons.

Compared with poly(allyl alcohol), the allyl ester copolymers of theinvention are soluble in a broader range of organic solvents (see Table1, below). Poly(allyl alcohol) is generally soluble in alcohols, but isnot soluble in many commonly used organic solvents such as ethers,esters, ketones, and hydrocarbons. In contrast, the allyl estercopolymers of the invention are soluble in a broad range of solvents.The favorable solubility characteristics of these copolymers giveformulators of adhesives, coatings, elastomers, and sealants greaterflexibility.

Allyl ester copolymers are useful in a variety of applications,including, for example, polyesters, polyurethanes, alkyds, uralkyds,acrylates, melamine resins, and other thermoset polymers. These uses aredescribed in more detail below, and in the examples.

The invention includes thermoset polyesters that are the reactionproducts of the allyl ester copolymers of the invention and an anhydrideor a di- or polycarboxylic acid. The use of such a reaction to prepare athermoset polyester coating from an allyl alcohol/allyl acetatecopolymer is shown in Example 9 below. Suitable anhydrides andcarboxylic acids are those commonly used in the polyester industry.Examples include, but are not limited to, phthalic anhydride, phthalicacid, maleic anhydride, maleic acid, adipic acid, isophthalic acid,terephthalic acid, sebacic acid, succinic acid, trimellitic anhydride,and the like, and mixtures thereof. Other suitable methods for makingthermoset polyesters are described in U.S. Pat. No. 3,457,324, theteachings of which are incorporated herein by reference.

A polyurethane composition is made by reacting an allyl ester copolymerof the invention with a di- or polyisocyanate or anisocyanate-terminated prepolymer. Prepolymers derived from the allylester copolymers of the invention can be used. Optionally, a lowmolecular weight chain extender (diol, diamine, or the like) isincluded. Suitable di- or polyisocyanates are those well known in thepolyurethane industry, and include, for example, toluene diisocyanate,MDI, polymeric MDIs, carbodiimide-modified MDIs, hydrogenated MDIs,isophorone diisocyanate, and the like. Isocyanate-terminated prepolymersare made in the usual way from a polyisocyanate and a polyether polyol,polyester polyol, or the like. The polyurethane is formulated at anydesired NCO index. If desired, all of the available NCO groups arereacted with hydroxy groups from the allyl ester copolymers and anychain extenders. Alternatively, an excess of NCO groups remain in theproduct, as in a moisture-cured polyurethane. Many types of polyurethaneproducts can be made, including, for example, adhesives, sealants,coatings, and elastomers. Example 10 illustrates a non-solventpolyurethane adhesive prepared from an isocyanate-terminated prepolymerand an allyl ester copolymer of the invention. Other suitable methodsfor making polyurethane compositions are described in U.S. Pat. No.2,965,615, the teachings of which are incorporated herein by reference.

The invention includes alkyd compositions prepared by reacting an allylester copolymer of the invention with an unsaturated fatty acid.Suitable unsaturated fatty acids are those known in the art as usefulfor alkyd resins, and include, for example, oleic acid, ricinoleic acid,linoleic acid, licanic acid, and the like, and mixtures thereof.Mixtures of unsaturated fatty acids and saturated fatty acids such aslauric acid or palmitic acid can also be used. The alkyd resins areparticularly useful for making alkyd coatings. For example, an allylester copolymer, or a mixture of an allyl ester copolymer and glycerinor another low molecular weight polyol, is first partially esterifiedwith an unsaturated fatty acid to give an alkyd resin. The resin is thencombined with an organic solvent, and the resin solution is stored untilneeded. A drying agent such as lead acetate or cobalt acetate is addedto the solution of alkyd resin, the solution is spread onto a surface,the solvent evaporates, and the resin cures leaving an alkyd coating ofthe invention. Example 12 below shows one way to make an alkyd coatingof the invention. Other suitable methods for making alkyd resins andcoatings are described in U.S. Pat. No. 3,423,341, the teachings ofwhich are incorporated herein by reference.

Instead of combining the alkyd resin with an organic solvent, the resincan be dispersed in water to make a water-based alkyd coatingformulation. To improve the water dispersability of the alkyd resin, afree hydroxyl group in the alkyd resin can be converted to a salt. Forexample, the alkyd resin can be reacted with phthalic anhydride to givea resin that contains phthalic acid residues; addition of sodiumhydroxide makes the sodium phthalate salt, and provides awater-dispersable alkyd resin derived from the allyl ester copolymer.See, for example, U.S. Pat. No. 3,483,152.

The invention includes polyurethane-modified alkyds (uralkyds) preparedfrom the allyl ester copolymers. These resins are especially valuablefor making uralkyd coatings. The allyl ester copolymer is firstpartially esterified with an unsaturated fatty acid (described above) togive an alkyd resin. The alkyd resin, which contains some free hydroxylgroups, is reacted with a di- or polyisocyanate (described above) togive a prepolymer. The prepolymer is then reacted with a chain extender,atmospheric moisture, or additional alkyd resin to give a uralkydcoating. Other suitable methods for making uralkyd resins and coatingsare described in U.S. Pat. No. 3,267,058, the teachings of which areincorporated herein by reference.

The invention includes thermoset polymers prepared by reacting the allylester copolymers of the invention with a thermoplastic polymer or acrosslinking agent. For example, melamine-based polymers, especiallycoatings, can be prepared by reacting the allyl ester copolymers withmelamine resins. Suitable melamine resins include commercial gradehexamethoxymethylmelamines, such as, for example, CYMEL 303 crosslinkingagent, a product of American Cyanamid Company. Example 8 belowillustrates the preparation of a melamine coating from an allylalcohol/allyl acetate copolymer. A thermoset resin is obtained byreacting the allyl ester copolymers of the invention with acrosslinkable thermoplastic resin. Suitable crosslinkable thermoplasticresins are anhydride or carboxylic acid-containing polymers such as, forexample, polyacrylic acid, polymethacrylic acid, isobutylene-maleicanhydride copolymers, and styrene-maleic anhydride copolymers. Example11 below illustrates the preparation of a crosslinked polymeric film ofthis type from an an allyl alcohol/allyl acetate copolymer and astyrene-maleic anhydride copolymer.

An acrylate composition of the invention is prepared by reacting some orall of the hydroxyl groups of the allyl ester copolymers with an acrylicacid or acrylic acid derivative. Suitable acrylic acids and derivativesinclude acrylic acid, methacrylic acid, acryloyl chloride, methacryloylchloride, methyl acrylate, methyl methacrylate, and the like. Example 13below illustrates this application. Suitable methods for preparingacrylates are described, for example, in U.S. Pat. No. 2,917,538, theteachings of which are incorporated herein by reference.

The favorable solubility characteristics of the allyl ester copolymersof the invention make them well-suited for blending with other polymers.The copolymers of the invention are easily blended with, for example,polyether polyols, phenolic resins, acrylates, and epoxy resins, and theblends can be used in the applications described earlier. The allylester copolymers can also be used as compatibilizers to improve themiscibility of polymer mixtures. In contrast, poly(allyl alcohol) isgenerally not compatible with other polymers, and cannot be blended withpolymers or used as a compatibilizer for other polymers.

The following examples merely illustrate the invention. Those skilled inthe art will recognize many variations that are within the spirit of theinvention and scope of the claims.

EXAMPLE 1 Preparation of Allyl Alcohol/Allyl Acetate Copolymer

Allyl alcohol (200 g), allyl acetate (200 g), and di-tert-butylperoxide(10 g) are charged to a one-liter stainless-steel reactor equipped withan addition pump, stirrer, steam heating jacket, temperature controller,nitrogen inlet, and vacuum distillation apparatus. The reactor is purgedthree times with nitrogen, is sealed, and the contents are heated to150° C. Di-tert-butylperoxide (40 g) is added continuously to thereactor using the addition pump over 2.5 h. Polymerization continues at150° C. for an additional 2 h. Unreacted monomers are removed by vacuumdistillation. The last traces of residual monomer are removed bystripping with water.

The yield of clear, slightly yellow liquid copolymer is 166 g (41.5%).Hydroxyl number=350 mg KOH/g. Gel permeation chromatography (GPC) usingpolystyrene standards shows that the product has Mw=1081, Mn=708, andMw/Mn=1.52.

EXAMPLE 2 Preparation of Allyl Alcohol/Allyl Acetate Copolymer

The procedure of Example 1 is generally followed with allyl alcohol (120g), allyl acetate (600 g), and tert-butylhydroperoxide (70% in water, 23g) as the initiator. After purging the reactor with nitrogen and sealingit, the contents are heated to 150° C. Additional 70% aq.tertobutylhydroperoxide (80 g) is added continuously to the reactorusing the addition pump over 4 h. Polymerization continues at 150° C.for an additional 0.5 h. Unreacted monomers are removed by vacuumdistillation. The last traces of residual monomer are removed bystripping with water.

The yield of clear, slightly yellow liquid copolymer is 310 g (43.1%).Hydroxyl number=107 mg KOH/g. GPC analysis: Mw=1248, Mn=778, andMw/Mn=1.60.

EXAMPLE 3 Preparation of Allyl Alcohol/Allyl Butyrate Copolymer

The procedure of Example 1 is generally followed with allyl alcohol (120g), allyl butyrate (600 g), and tert-butylhydroperoxide (70% in water,23 g). After purging the reactor with nitrogen and sealing it, thecontents are heated to 150° C. Additional 70% aq.tert-butylhydroperoxide (80 g) is added continuously to the reactorusing the addition pump over 4 h. Polymerization continues at 150° C.for an additional 0.5 h. Unreacted monomers are removed by vacuumdistillation. The last traces of residual monomer are removed bystripping with water.

The yield of clear, slightly yellow liquid copolymer is 402 g (55.9%).Hydroxyl number=93 mg KOH/g. GPC analysis: Mw=1811, Mn=1103, andMw/Mn=1.64.

EXAMPLE 4 Preparation of Allyl Alcohol/Allyl Butyrate Copolymer

The procedure of Example 1 is generally followed with allyl alcohol (60g), allyl butyrate (600 g), and di-tert-butylperoxide (6.0 g). Thereactor is purged three times with nitrogen, is sealed, and the contentsare heated to 150° C. Di-tert-butylperoxide (60 g) is added continuouslyto the reactor using the addition pump over 5 h. Polymerizationcontinues at 150° C. for an additional 0.5 h. Unreacted monomers areremoved by vacuum distillation. The last traces of residual monomer areremoved by stripping with water.

The yield of clear, slightly yellow liquid copolymer is 476 g (72.2%).Hydroxyl number=48 mg KOH/g. GPC analysis: Mw=2220, Mn=1270, andMw/Mn=1.75.

EXAMPLE 5 Preparation of Propoxylated Allyl Alcohol/Allyl AcetateCopolymer

The procedure of Example 1 is generally followed with propoxylated allylalcohol (average of 1.6 oxypropylene units; 300 g), allyl acetate (300g), and di-tertbutylperoxide (20 g). The reactor is purged three timeswith nitrogen, is sealed, and the contents are heated to 150° C.Di-tert-butylperoxide (80 g) is added continuously to the reactor usingthe addition pump over 4 h. Polymerization continues at 150° C. for anadditional 0.5 h. Unreacted monomers are removed by vacuum distillation.The last traces of residual monomer are removed by stripping with water.

The yield of clear, slightly yellow liquid copolymer is 420 g (70.0%).Hydroxyl number=127 mg KOH/g. GPC analysis: Mw=1810, Mn=1040, andMw/Mn=1.73.

COMPARATIVE EXAMPLE 6 Preparation of Poly(allyl alcohol)

The procedure of Example 1 is generally followed to make poly(allylalcohol). Allyl alcohol (432 g) and tert-butylperoxide (6 g) areinitially charged to the reactor. The remaining tert-butylperoxide (60g) is added to the reactor at 150° C. over 5 h. Polymerization continuesat 150° C. for an additional 0.5 h. Unreacted monomers are removed byvacuum distillation. The last traces of residual monomer are removed bystripping with water.

The yield of viscous clear, slightly yellow liquid copolymer is 121 g(28.0%). Carbon-13 NMR analysis shows that the product is a homopolymerof allyl alcohol. Hydroxyl number and GPC analysis are not obtainedbecause the product is not soluble in the solvents used for analysis.

EXAMPLE 7 Solubility Testing of Allylic Alcohol/Allyl Ester Copolymers

The solubility of the polymers obtained in Examples 1-5 and ComparativeExample 6 is tested in a variety of common organic solvents, includingisopropyl alcohol, propylene glycol tert-butyl ether, tetrahydrofuran,acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate,xylenes, and cyclohexane. Results appear in Table 1. Solubility istested by mixing 10 wt. % of the polymer in the solvent to give a clearsolution (soluble=sol), a cloudy solution (partly soluble=p. sol), ortwo distinct layers (insoluble=insol).

The results suggest that the copolymers of the invention, because theyhave good solubility in a broad range of common organic solvents, willbe easy to formulate into many end uses, especially when compared withpoly(allyl alcohol).

EXAMPLE 8 Melamine Coatings from an Allyl Alcohol/Allyl AcetateCopolymer

The allyl alcohol/allyl acetate copolymer of Example 2 is formulatedinto melamine coatings as follows. The copolymer (45 g) is mixed withCYMEL 303 melamine resin (15 g, product of American Cyanamid),p-toluenesulfonic acid (0.06 g), methyl ethyl ketone (9 g), and ethylacetate (9 g). The solution is coated onto aluminum Q-panels (AI-35,Paul N. Gardner Co., Inc.) at a wet thickness of about 3 mils. Thecoated panels are dried in a hood for 12 h at room temperature, and arethen cured in an oven at 110° C. to 120° C. for 15 to 90 min.. Thecoatings show good hardness, adhesion, and flexibility properties.

EXAMPLE 9 Preparation of a Thermoset Polyester Coating

In this example, an allyl alcohol/allyl acetate copolymer is formulatedinto a thermosetting polyester coating. An allyl alcohol/allyl acetatecopolymer (500 g, prepared as in Example 1) and isophthalic acid (94 g)are charged into a reactor and heated to 220° C. while sparging nitrogenthrough the mixture. After the acid number reaches 60-70 mg KOH/g,adipic acid (73 g), isophthalic acid (60 g), and maleic anhydride (6 g)are added, and the mixture is reheated to 220° C. Heating continues at220° C. until the acid number drops to 10-12 mg KOH/g. 2-Ethoxyethanolacetate (270 g) is then added.

Six hundred grams of the resulting polyester solution is charged into areactor equipped with an agitator, thermometer, reflux condenser,addition funnel, and nitrogen inlet, and the mixture is heated to 120°C. A mixture of 2-hydroxyethyl acrylate (10 g), ethyl acrylate (54 g),styrene (5 g), methyl methacrylate (20 g), methacrylic acid (2 g), anddi-t-butylperoxide (1.0 g) is charged to the addition funnel. Theacrylate monomer mixture is added to the polyester mixture over 2 h, andis then kept at 120° C. for another hour. t-Butyl perbenzoate (0.2 g) isadded, and the mixture is kept at 120° C. for another 2 h. A second 0.2g portion of t-butyl perbenzoate is added, and heating continues foranother 2 h. The product solution is finally diluted with 1-butanol (30g) and xylene (20 g). This solution is expected to be useful as athermosettable coating. The solution can be applied as a film, andallowed to cure at room temperature or elevated temperature.

EXAMPLE 10 Preparation of a Non-Solvent Polyurethane Adhesive

This example illustrates the preparation of a non-solvent polyurethaneadhesive by reacting an allyl alcohol/allyl acetate copolymer with anisocyanate-terminated prepolymer.

An allyl alcohol/allyl acetate copolymer (10 g, prepared as in Example1), is mixed well at room temperature with 10 g of a prepolymer (5.7 wt.% NCO) prepared from ARCOL 3020 polyether triol (2000 mol. wt., all-POtriol, product of ARCO Chemical Co.), and toluene diisocyanate. Theresulting adhesive mixture is expected to be useful for bonding wood,stainless steel, glass, and polystyrene plastic.

EXAMPLE 11 Preparation of a Crosslinked Polymer Film

In this example, an allyl alcohol/allyl acetate copolymer is used tomake a crosslinked polymer film.

DYLARK 378 resin (a terpolymer of styrene (67%), maleic anhydride (13%),and butadiene rubber (20%), product of ARCO Chemical Co., 10 g), and theallyl alcohol/allyl acetate copolymer of Example 1 (1.5 g) are dissolvedin tetrahydrofuran (50 g). The solution is spread and dried on analuminum pan. The resulting polymer film is cured at 200° C. for 0.5 h.The expected product is a cured, thermoset polymer film.

EXAMPLE 12 Preparation of an Alkyd Coating

In this example, an alkyd coating is prepared from an allylalcohol/allyl acetate copolymer.

The allyl alcohol/allyl acetate copolymer of Example 1 (87 g), saffloweroil (64 g), lithium hydroxide (0.03 g), phthalic anhydride (25.5 g),maleic anhydride (0.22 g), triphenyl phosphite (0.07 g), and xylene (18g) are charged into a reactor equipped with an agitator, thermometer,reflux condenser with a Dean-Stark trap, and nitrogen inlet. The mixtureis heated to 240° C., and is kept at that temperature until the acidnumber drops to 10-20 mg KOH/g. After the reaction, xylene is added todilute the mixture to 50 wt. % solids. This solution is expected to beuseful as an alkyd coating. The solution can be applied as a film, andallowed to cure at room temperature or at elevated temperature.

EXAMPLE 13 Preparation of a Curable Acrylate Composition

In this example, a curable acrylate composition is prepared from anallyl alcohol/allyl acetate copolymer.

The allyl alcohol/allyl acetate copolymer of Example 2 (100 g), acrylicacid (13.8 g), toluene (20 g), hydroquinone (0.15 g), and sulfuric acid(0.15 g), are charged into a reactor equipped with an agitator,thermometer, reflux condenser with Dean-Stark trap, and nitrogen inlet.The mixture is heated to reflux (about 100° C. to 115° C.), and water(3.4 g) is removed using the trap. After no additional water is beingproduced, the toluene is removed by vacuum distillation. The expectedproduct is a copolymer of allyl alcohol and allyl acetate in which mostor all of the hydroxyl groups from the original copolymer are convertedto acrylate ester groups.

                                      TABLE 1                                     __________________________________________________________________________    Solubility of Allylic Alcohol/Allyl Ester Copolymers in Common Organic        Solvents                                                                               Ex. 1                                                                              Ex. 2                                                                              Ex. 3                                                                              Ex. 4                                                                              Ex. 5 Comp. Ex. 6                                         AA/AAc                                                                             AA/AAc                                                                             AA/ABu                                                                             AA/ABu                                                                             AAP/AAc                                                                             poly(AA)                                   __________________________________________________________________________    isopropyl                                                                              sol  sol  sol  sol  sol   sol                                        alcohol                                                                       propylene glycol                                                                       sol  sol  sol  sol  sol   insol                                      t-butyl ether                                                                 tetrahydrofuran                                                                        sol  sol  sol  sol  sol   insol                                      acetone  sol  sol  sol  sol  sol   insol                                      methyl ethyl                                                                           sol  sol  sol  sol  sol   insol                                      ketone                                                                        methyl isobutyl                                                                        sol  sol  sol  sol  sol   insol                                      ketone                                                                        ethyl acetate                                                                          sol  sol  sol  sol  sol   insol                                      xylenes  sol  sol  sol  sol  sol   insol                                      cyclohexane                                                                            insol                                                                              insol                                                                              p. sol                                                                             sol  insol insol                                      __________________________________________________________________________     Solubility is tested by mixing 10 wt. % polymer in the solvent to give a      clear solution (sol), a cloudy solution (p. sol), or two distinct layers      (insol).                                                                      AA/AAc = allyl alcohol/allyl acetate copolymer;                               AA/ABu = allyl alcohol/allyl butyrate copolymer;                              AAP/AAc = propoxylated allyl alcohol/allyl acetate copolymer; poly(AA) =      poly(allyl alcohol).                                                     

I claim:
 1. A copolymer which consists essentially of recurring unitsof:(a) an allyl ester of the formula CH₂ =CR'-CH₂ -O-CO-R in which R ishydrogen or a saturated linear, branched, or cyclic C₁ -C₃₀ alkyl, aryl,or aralkyl group, and R' is selected from the group consisting ofhydrogen and C₁ -C₅ alkyl; and (b) an allylic alcohol of the formula CH₂=CR'-CH₂ -OH in which R' is selected from the group consisting ofhydrogen and C₁ -C₅ alkyl; wherein the copolymer has an average hydroxylfunctionality within the range of about 2 to about 10, and a numberaverage molecular weight within the range of about 300 to about 15,000.2. The copolymer of claim 1 having from about 5 to about 95 wt. % ofallyl ester recurring units and from about 95 to about 5 wt. % ofallylic alcohol recurring units.
 3. The copolymer of claim 1 having ahydroxyl number within the range of about 10 mg KOH/g to about 950 mgKOH/g.
 4. The copolymer of claim 1 wherein the allyl ester has theformula CH₂ =CH-CH₂ -O-CO-R in which R is a C₁ -C₅ alkyl group.
 5. Thecopolymer of claim 1 wherein the allylic alcohol is selected from thegroup consisting of allyl alcohol and methallyl alcohol.
 6. Thecopolymer of claim 1 having a number average molecular weight within therange of about 500 and about 3000, and a hydroxyl number within therange of about 25 mg KOH/g to about 500 mg KOH/g.